Title: A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

Journal Article · · Angewandte Chemie
 [1];  [2];  [3];  [4];  [2]; ORCiD logo [1]
  1. Department of Chemistry University of California, Riverside Riverside CA 92521 USA
  2. Department of Chemistry Iowa State University Ames IA 50011 USA, U.S. Department of Energy Ames Laboratory Ames IA 50011 USA
  3. U.S. Department of Energy Ames Laboratory Ames IA 50011 USA, CNRS Laboratoire de Chimie de la Matière Condensée de Paris Sorbonne Université, LCMCP 75005 Paris France
  4. U.S. Department of Energy Ames Laboratory Ames IA 50011 USA
+ Show Author Affiliations

Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1855301
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 20 Vol. 134; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (78)

Highly Robust Palladium(II) α-Diimine Catalysts for Slow-Chain-Walking Polymerization of Ethylene and Copolymerization with Methyl Acrylate journal June 2015
Direct Synthesis of Functionalized High-Molecular-Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers journal October 2016
A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit journal July 2017
Die Schöne (WCA) und das (kationische) Biest: Neues aus der Chemie von und mit schwach koordinierenden Anionen journal September 2018
Activation of C−F Bonds by Electrophilic Organosilicon Sites Supported on Sulfated Zirconia journal October 2018
Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers journal May 2019
Uranocenium: Synthesis, Structure, and Chemical Bonding journal June 2019
Hydrogen‐Bonding‐Induced Heterogenization of Nickel and Palladium Catalysts for Copolymerization of Ethylene with Polar Monomers journal June 2021
Highly Robust Palladium(II) α-Diimine Catalysts for Slow-Chain-Walking Polymerization of Ethylene and Copolymerization with Methyl Acrylate journal June 2015
Direct Synthesis of Functionalized High-Molecular-Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers journal October 2016
A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit journal July 2017
Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions journal September 2018
Activation of C−F Bonds by Electrophilic Organosilicon Sites Supported on Sulfated Zirconia journal October 2018
Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers journal May 2019
Uranocenium: Synthesis, Structure, and Chemical Bonding journal June 2019
Hydrogen‐Bonding‐Induced Heterogenization of Nickel and Palladium Catalysts for Copolymerization of Ethylene with Polar Monomers journal June 2021
The Effect of Counterion/Ligand Interplay on the Activity and Stereoselectivity of Palladium(II)–Diimine Catalysts for CO/p-Methylstyrene Copolymerization journal February 2007
Phase-modulated LA-REDOR: A robust, accurate and efficient solid-state NMR technique for distance measurements between a spin-1/2 and a quadrupole spin journal July 2014
Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts journal March 2016
Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts journal April 2021
From Multisite Polymerization Catalysis to Sustainable Materials and All-Polyolefin Composites journal September 2015
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities journal January 2016
Quantification of Activated Single-Site Olefin Polymerization Catalysts on a Solid Support journal December 2015
A Well-Defined Ni(II) α-Diimine Catalyst Supported on Sulfated Zirconia for Polymerization Catalysis journal June 2017
A Bulky Pd(II) α-Diimine Catalyst Supported on Sulfated Zirconia for the Polymerization of Ethylene and Copolymerization of Ethylene and Methyl Acrylate journal February 2018
Solid-State 45 Sc NMR Studies of Cp* 2 Sc–OR (R = CMe 2 CF 3 , CMe(CF 3 ) 2 , C(CF 3 ) 3 , SiPh 3 ) and Relationship to the Structure of Cp* 2 Sc-Sites Supported on Partially Dehydroxylated Silica journal February 2020
Nontraditional Catalyst Supports in Surface Organometallic Chemistry journal September 2020
Palladium and Nickel Catalyzed Chain Walking Olefin Polymerization and Copolymerization journal December 2015
Chromophore Quench-Labeling: An Approach to Quantifying Catalyst Speciation As Demonstrated for (EBI)ZrMe 2 /B(C 6 F 5 ) 3 -Catalyzed Polymerization of 1-Hexene journal October 2016
Alkynyl Ether Labeling: A Selective and Efficient Approach to Count Active Sites of Olefin Polymerization Catalysts journal February 2019
Active Sites in a Heterogeneous Organometallic Catalyst for the Polymerization of Ethylene journal July 2021
Design Strategies for the Molecular Level Synthesis of Supported Catalysts journal August 2011
Ortho -Phosphinobenzenesulfonate: A Superb Ligand for Palladium-Catalyzed Coordination–Insertion Copolymerization of Polar Vinyl Monomers journal April 2013
Ion Pairing in Transition-Metal Organometallic Chemistry journal June 2005
“Bound but Not Gagged”Immobilizing Single-Site α-Olefin Polymerization Catalysts journal November 2005
Coordination−Insertion Copolymerization of Fundamental Polar Monomers journal November 2009
Late-Metal Catalysts for Ethylene Homo- and Copolymerization journal April 2000
Heterogeneous Single-Site Catalysts for Olefin Polymerization journal April 2000
Solid-Supported Single-Component Pd(II) Catalysts for Polar Monomer Insertion Copolymerization journal July 2014
Supported Metallocene Catalysts by Surface Organometallic Chemistry. Synthesis, Characterization, and Reactivity in Ethylene Polymerization of Oxide-Supported Mono- and Biscyclopentadienyl Zirconium Alkyl Complexes:  Establishment of Structure/Reactivity Relationships journal April 2001
Mechanistic Studies of Pd(II)−α-Diimine-Catalyzed Olefin Polymerizations 1 journal July 2000
Supported organoactinides. High-resolution solid-state carbon-13 NMR studies of catalytically active, alumina-bound pentamethylcyclopentadienyl)thorium methyl and hydride complexes journal February 1985
A 2 H-Labeling Scheme for Active-Site Counts in Metallocene-Catalyzed Alkene Polymerization journal March 2001
Computational Insights on the Challenges for Polymerizing Polar Monomers journal July 2002
Perhydrocarbyl Re VII Complexes: Comparison of Molecular and Surface Complexes journal January 2003
Synthesis, Spectroscopy, and Catalytic Properties of Cationic Organozirconium Adsorbates on “Super Acidic” Sulfated Alumina. “Single-Site” Heterogeneous Catalysts with Virtually 100 Active Sites journal April 2003
Detailed Structural Investigation of the Grafting of [Ta(CH t Bu)(CH 2 t Bu) 3 ] and [Cp*TaMe 4 ] on Silica Partially Dehydroxylated at 700 °C and the Activity of the Grafted Complexes toward Alkane Metathesis journal October 2004
Proton-Selective 17 O− 1 H Distance Measurements in Fast Magic-Angle-Spinning Solid-State NMR Spectroscopy for the Determination of Hydrogen Bond Lengths journal November 2006
Borane-Induced Dehydration of Silica and the Ensuing Water-Catalyzed Grafting of B(C 6 F 5 ) 3 To Give a Supported, Single-Site Lewis Acid, ≡SiOB(C 6 F 5 ) 2 journal December 2011
17 O NMR Gives Unprecedented Insights into the Structure of Supported Catalysts and Their Interaction with the Silica Carrier journal May 2012
A Robust Ni(II) α-Diimine Catalyst for High Temperature Ethylene Polymerization journal October 2013
Olefin Isomerization and Hydrosilylation Catalysis by Lewis Acidic Organofluorophosphonium Salts journal November 2013
Links Between Single-Site Heterogeneous and Homogeneous Catalysis. DFT Analysis of Pathways for Organozirconium Catalyst Chemisorptive Activation and Olefin Polymerization on γ-Alumina journal November 2008
Single-Site Organozirconium Catalyst Embedded in a Metal–Organic Framework journal December 2015
The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy journal March 2016
Synthesis and Electronic Structures of Heavy Lanthanide Metallocenium Cations journal December 2017
Electron-Rich Metal Cations Enable Synthesis of High Molecular Weight, Linear Functional Polyethylenes journal June 2018
Highly Active Supported Nickel Diimine Catalysts for Polymerization of Ethylene journal July 2002
MgCl 2 -Based Supports for the Immobilization and Activation of Nickel Diimine Catalysts for Polymerization of Ethylene journal July 2004
Efficient Slurry-Phase Homopolymerization of Ethylene to Branched Polyethylenes Using α-Diimine Nickel(II) Catalysts Covalently Linked to Silica Supports journal August 2006
A Well-Defined, Silica-Supported Tungsten Imido Alkylidene Olefin Metathesis Catalyst journal July 2006
Mechanism of the Reaction of Vinyl Chloride with (α-diimine)PdMe + Species journal March 2010
The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalysts † journal November 2010
Increasing the Reactivity of Vaska’s Compound. Oxidative Addition of Chlorobenzene at Ambient Temperature journal February 2008
Neutral and Cationic Palladium(II) Bis(pyrazolyl)methane Complexes journal October 1999
Molecular magnetic hysteresis at 60 kelvin in dysprosocenium journal August 2017
Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning journal April 2018
Measuring multiple carbon–nitrogen distances in natural abundant solids using R-RESPDOR NMR journal January 2006
Hydrosilane-B(C 6 F 5 ) 3 adducts as activators in zirconocene catalyzed ethylene polymerization journal January 2016
Electronic structures of bent lanthanide(III) complexes with two N-donor ligands journal January 2019
Al(OR F ) 3 (R F = C(CF 3 ) 3 ) activated silica: a well-defined weakly coordinating surface anion journal January 2020
Highly active metallocene catalysts for olefin polymerization journal January 1998
Supported cationic complexes: selective preparation and characterization of the well-defined electrophilic metallocenium cation [SiO–B(C 6 F 5 ) 3 ] − [Cp*ZrMe 2 (Et 2 NPh)] + supported on silica journal January 2003
Measurement of hetero-nuclear distances using a symmetry-based pulse sequence in solid-state NMR journal January 2010
Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst journal January 2010
Silica-supported single-site catalysts: to be or not to be? A conjecture on silica surfaces journal January 2011
Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites journal December 2012
Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet journal October 2018

Similar Records

Related Subjects